Transition metal compound, catalyst for addition polymerization, and process for producing addition polymer

ABSTRACT

A transition metal compound (A) of the formula (1), a catalyst for addition polymerization obtained by bringing the transitionmetal compound to contact with (B) and/or (C) below, and a process for producing an addition polymer with the catalyst:  
                 
 
     wherein, M represents a titanium atom, zirconium atom or hafnium atom in the +3 formal oxide condition; A represents a multidentate mono-anionic ligand; R 1  represents an alkyl group, aralkyl group, aryl group or substituted silyl group; E represents an oxygen atom or sulfur atom; each of two Xs independently represents a hydrogen atom, halogen atom, alkyl group, aralkyl group, aryl group, substituted silyl group, alkoxy group, aralkyloxy group, aryloxy group or di-substituted amino group, and two Xs may bond mutually to form a ring; D represents a neutral ligand coordinated on M; and n represents an integer of from 0 to 2.), (B)Organic aluminum compound and/or aluminoxane, (C)Specific boron compound.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a transition metal compoundhaving a multidentate mono-anionic ligand containing a hetero atom as asubstituent, a catalyst for addition polymerization obtained by usingsaid transition metal compound, and a process for producing an additionpolymer with the catalyst.

[0003] 2. Description of Related Arts

[0004] Regarding a method for producing an addition polymer with asingle site catalyst composed of a metallocene complex or the like, manyreports have done. For example, JP-A-58-19309 discloses a method forproducing an olefin polymer with a metallocene complex and analuminoxane. There has been a problem that when addition polymerizationof an olefin or the like is conducted in such a system, the amount ofthe initial heat generation is large particularly due to high initialactivity and consequently control of the polymerization reaction isdifficult.

SUMMARY OF THE INVENTION

[0005] Under the above-situation, an object of the present invention isto provide a transition metal compound useful for preparing a catalystfor addition polymerization having a catalytic activity which suppressesheat generation at the beginning of polymerization and can beindustrially carried out, and such a catalyst for additionpolymerization, and an efficient process for producing an additionpolymer, which can suppress heat generation at the beginning ofpolymerization and can be industrially carried out.

[0006] Namely, the present invention relates to a transition metalcompound (A) of the following general formula (1):

[0007] (wherein, M represents a titanium atom, zirconium atom or hafniumatom in the +3 formal oxide condition; A represents a multidentatemono-anionic ligand; R¹ represents an alkyl group, aralkyl group, arylgroup or substituted silyl group; E represents an oxygen atom or sulfuratom; each of two Xs independently represents a hydrogen atom, halogenatom, alkyl group, aralkyl group, aryl group, substituted silyl group,alkoxy group, aralkyloxy group, aryloxy group or di-substituted aminogroup, and two Xs may bond mutually to form a ring; D represents aneutral ligand coordinated on M; and n represents an integer of from 0to 2.). Further, the present invention relates to a catalyst foraddition polymerization obtained by bringing the transition metalcompound (A) into contact with the following (B) and/or (C):

[0008] (B) one or more aluminum compounds selected from the following(B1) to (B3);

[0009] (B1) organic aluminum compounds of the general formula E¹_(a)AlZ_(3−a),

[0010] (B2) cyclic aluminoxanes having a structure of the generalformula {—Al(E²)—O—}_(b), and

[0011] (B3) linear aluminoxanes having a structure of the generalformula E³{—Al(E³)—O—}_(c)AlE³ ₂ (wherein, each of E¹, E² and E³represents a hydrocarbon group, and all E¹s, all E²s or all E³s may bethe same or different. Z represents a hydrogen atom or halogen atom, andall Zs may be the same or different. a represents a number satisfying0<a<3, b represents an integer of 2 or more, and c represents an integerof 1 or more.),

[0012] (C) one or more boron compounds selected from the following (C1)to (C3):

[0013] (C1) boron compounds of the general formula BQ¹Q²Q³,

[0014] (C2) boron compounds of the general formula G⁺(BQ¹Q²Q³Q⁴)⁻, and

[0015] (C3) boron compounds of the general formula(L-H)⁺(BQ¹Q²Q³Q⁴)⁻(wherein, B represents a trivalent boron atom, and Q¹to Q⁴ represent a halogen atom, hydrocarbon group, halogenatedhydrocarbon group, substituted silyl group, alkoxy group ordi-substituted amino group, and they may be the same or different. G⁺represents an inorganic or organic cation, and L represents a neutralLewis base and (L-H)⁺ represents a Brφnsted acid.).

BRIEF DESCRIPTION OF THE DRAWING

[0016]FIG. 1 is a flow chart for assisting understanding of the presentinvention. This flow chart shows a typical example of embodiments of thepresent invention, and the scope of the present invention is not limitedat all thereto.

DETAILED DESCRIPTION OF THE INVENTION

[0017] The present invention will be illustrated in detail below.

[0018] In the transition metal compound (A) of the above-mentionedgeneral formula (1), M represents a titanium atom, zirconium atom orhafnium atom in the +3 formal oxidation state, and particularlypreferably a titanium atom in the +3 formal oxidation state.

[0019] Examples of the neutral ligand represented by D coordinated on M,in the general formula (1), include, for example, ether compounds suchas diethyl ether, tetrahydrofuran, di-n-butyl ether, di-iso-butyl ether,di-tert-butyl ether and the like, tertiary amine compounds such astriethylamine, pyridine and the like, nitrile compounds such asacetonitrile, benzonitrile and the like, etc., and preferablytetrahydrofuran and pyridine.

[0020] E in the general formula (1) is an oxygen atom or sulfur atom,and preferably an oxygen atom.

[0021] As the halogen atom represented by X in the general formula (1),a fluorine atom, chlorine atom, bromine atom, iodine atom and the likeare exemplified, and particularly preferable is a chlorine atom.

[0022] As the alkyl group represented by X or R¹ in the general formula(1), an alkyl group having 1 to 20 carbon atoms is preferable, andexamples thereof include a methyl group, ethyl group, n-propyl group,isopropyl group, n-butyl group, sec-butyl group, tert-butyl group,isobutyl group, n-pentyl group, neopentyl group, amyl group, n-hexylgroup, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecylgroup, n-eicosyl group and the like, and more preferable examples are amethyl group, ethyl group, isopropyl group, tert-butyl group, isobutylgroup and amyl group.

[0023] Any of these alkyl groups may be substituted with a halogen atomsuch as a fluorine atom, chlorine atom, bromine atom, iodine atom andthe like. Examples of the alkyl group having 1 to 10 carbon atomssubstituted with a halogen atom include a fluoromethyl group,difluoromethyl group, trifluoromethyl group, chloromethyl group,dichloromethyl group, trichloromethyl group, bromomethyl group,dibromomethyl group, tribromomethyl group, iodomethyl group,diiodomethyl group, triiodomethyl group, fluoroethyl group,difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group,pentafluoroethyl group, chloroethyl group, dichloroethyl group,trichloroethyl group, tetrachloroethyl group, pentachloroethyl group,bromoethyl group, dibromoethyl group, tribromoethyl group,tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group,perfluorobutyl group, perfluoropentyl group, perfluorohexyl group,perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group,perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group,perchloropentyl group, perchlorohexyl group, perchlorooctyl group,perchlorododecyl group, perchloropentadecyl group, perchloroeicosylgroup, perbromopropyl group, perbromobutyl group, perbromopentyl group,perbromohexyl group, perbromooctyl group, perbromododecyl group,perbromopentadecyl group, perbromoeicosyl group and the like.

[0024] Further, any of these alkyl groups may also be partiallysubstituted with an alkoxy group such as a methoxy group, ethoxy groupand the like, an aryloxy group such as a phenoxy group and the like, anaralkyloxy group such as a benzyloxy group and the like, etc.

[0025] As the aralkyl group represented by X or R¹ in theabove-mentioned general formula (1), an aralkyl group having 7 to 20carbon atoms is preferable, and examples thereof include a benzyl group,(2-methylphenyl)methyl group,

[0026] (3-methylphenyl)methyl group, (4-methylphenyl)methyl group,

[0027] (2,3-dimethylphenyl)methyl group,

[0028] (2,4-dimethylphenyl)methyl group,

[0029] (2,5-dimethylphenyl )methyl group,

[0030] (2,6-dimethylphenyl)methyl group,

[0031] (3,4-dimethylphenyl)methyl group,

[0032] (3,5-dimethylphenyl)methyl group,

[0033] (2,3,4-trimethylphenyl)methyl group,

[0034] (2,3,5-trimethylphenyl)methyl group,

[0035] (2,3,6-trimethylphenyl)methyl group,

[0036] (3,4,5-trimethylphenyl)methyl group,

[0037] (2,4,6-trimethylphenyl)methyl group,

[0038] (2,3,4,5-tetramethylphenyl)methyl group,

[0039] (2,3,4,6-tetramethylphenyl)methyl group,

[0040] (2,3,5,6-tetramethylphenyl)methyl group,

[0041] (pentamethylphenyl)methyl group, (ethylphenyl)methyl group,

[0042] (n-propylphenyl)methyl group, (isopropylphenyl)methyl group,

[0043] (n-butylphenyl)methyl group, (sec-butylphenyl)methyl group,

[0044] (tert-butylphenyl)methyl group, (n-pentylphenyl)methyl group,(neopentylphenyl)methyl group, (n-hexylphenyl)methyl group,(n-octylphenyl)methyl group, (n-decylphenyl)methyl group,(n-dodecylphenyl)methyl group, naphthylmethyl group, anthracenylmethylgroup and the like, and a benzyl group is preferable.

[0045] Any of these aralkyl groups may also be partially substitutedwith a halogen atom such as a fluorine atom, chlorine atom, bromineatom, iodine atom and the like, an alkoxy group such as a methoxy group,ethoxy group and the like, an aryloxy group such as aphenoxy group andthe like, an aralkyloxy group such as a benzyloxy group and the like,etc.

[0046] As the aryl group represented by X or R¹ in the general formula(1), an aryl group having 6 to 20 carbon atoms is preferable, andexamples thereof include a phenyl group, 2-tolyl group, 3-tolyl group,4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group,2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenylgroup, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group,2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group,2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group,2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenylgroup, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group,sec-butylphenyl group, tert-butylphenyl group, di-tert-butylphenylgroup, di-tert-butylmethylphenyl group, n-pentylphenyl group,neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group,n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group,naphthyl group, anthracenyl group and the like, and a phenyl group ismore preferable.

[0047] Any of these aryl groups may also be partially substituted with ahalogen atom such as a fluorine atom, chlorine atom, bromine atom,iodine atom and the like, an alkoxy group such as a methoxy group,ethoxy group and the like, an aryloxy group such as a phenoxy group andthe like, an aralkyloxy group such as a benzyloxy group and the like,etc.

[0048] As the substituted silyl group represented by X or R¹ in thegeneral formula (1), a silyl group substituted with a hydrocarbon groupis preferable, and examples of the hydrocarbon group include alkylgroups having 1 to 10 carbon atoms such as a methyl group, ethyl group,n-propyl group, isopropyl group, n-butyl group, sec-butyl group,tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group,cyclohexyl group and the like, and aryl groups such as a phenyl groupand the like, etc. As such substituted silyl group having 1 to 20 carbonatoms, for example, mono-substituted silyl groups having 1 to 20 carbonatoms such as a methylsilyl group, ethylsilyl group, phenylsilyl groupand the like, di-substituted silyl groups having 2 to 20 carbon atomssuch as a dimethylsilyl group, diethylsilyl group, diphenylsilyl groupand the like, tri-substituted silyl groups having 3 to 20 carbon atomssuch as a trimethylsilyl group, triethylsilyl group, tri-n-propylsilylgroup, triisopropylsilyl group, tri-n-butylsilyl group,tri-sec-butylsilyl group, tri-tert-butylsilyl group, triisobutylsilylgroup, tert-butyldimethylsilyl group, tri-n-pentylsilyl group,tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl groupand the like, etc. are listed, and preferable are a trimethylsilylgroup, tert-butyldimethylsilyl group and triphenylsilyl group.

[0049] Any of these substituted silyl groups may also be partiallysubstituted with a halogen atom such as a fluorine atom, chlorine atom,bromine atom, iodine atom and the like, an alkoxy group such as amethoxy group, ethoxy group and the like, an aryloxy group such as aphenoxy group and the like, an aralkyloxy group such as a benzyloxygroup and the like, etc.

[0050] As the alkoxy group represented by X in the general formula (1),an alkoxy group having 1 to 20 carbon atoms is preferable, and examplesthereof include a methoxy group, ethoxy group, n-propoxy group,isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group,n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group,n-dodecoxy group, n-pentadecoxy group, n-icoxoxy group and the like, andmore preferable are a methoxy group, ethoxy group, isopropoxy group andtert-butoxy group.

[0051] Any of these alkoxy groups may also be partially substituted witha halogen atom such as a fluorine atom, chlorine atom, bromine atom,iodine atom and the like, an alkoxy group such as a methoxy group,ethoxy group and the like, an aryloxy group such as aphenoxy group andthe like, an aralkyloxy group such as a benzyloxy group and the like,etc.

[0052] As the aralkyloxy group represented by X in the general formula(1), an aralkyloxy group having 7 to 20 carbon atoms is preferable, andexamples thereof include a benzyloxy group,

[0053] (2-methylphenyl)methoxy group, (3-methylphenyl)methoxy group,(4-methylphenyl)methoxy group,

[0054] (2,3-dimethylphenyl)methoxy group,

[0055] (2,4-dimethylphenyl)methoxy group,

[0056] (2,5-dimethylphenyl)methoxy group,

[0057] (2,6-dimethylphenyl)methoxy group,

[0058] (3,4-dimethylphenyl)methoxy group,

[0059] (3,5-dimethylphenyl)methoxy group,

[0060] (2,3,4-trimethylphenyl)methoxy group,

[0061] (2,3,5-trimethylphenyl)methoxy group,

[0062] (2,3,6-trimethylphenyl)methoxy group,

[0063] (2,4,5-trimethylphenyl)methoxy group,

[0064] (2,4,6-trimethylphenyl)methoxy group,

[0065] (3,4,5-trimethylphenyl)methoxy group,

[0066] (2,3,4,5-tetramethylphenyl)methoxy group,

[0067] (2,3,4,6-tetramethylphenyl)methoxy group,

[0068] (2,3,5,6-tetramethylphenyl)methoxy group,

[0069] (pentamethylphenyl)methoxy group, (ethylphenyl)methoxy group,(n-propylphenyl ) methoxy group,

[0070] (isopropylphenyl)methoxy group, (n-butylphenyl )methoxy group,(sec-butylphenyl)methoxy group,

[0071] (tert-butylphenyl)methoxy group, (n-hexylphenyl)methoxy group,(n-octylphenyl)methoxy group, (n-decylphenyl)methoxy group,naphthylmethoxy group, anthracenylmethoxy group and the like, and morepreferable is a benzyloxy group.

[0072] Any of these aralkyloxy groups may also be partially substitutedwith a halogen atom such as a fluorine atom, chlorine atom, bromineatom, iodine atom and the like, an alkoxy group such as a methoxy group,ethoxy group and the like, an aryloxy group such as aphenoxy group andthe like, an aralkyloxy group such as a benzyloxy group and the like,etc.

[0073] As the aryloxy group represented by X in the general formula (1),an aryloxy group having 6 to 20 carbon atoms is preferable, and examplesthereof include a phenoxy group,

[0074] 2-methylphenoxy group, 3-methylphenoxy group,

[0075] 4-methylphenoxy group, 2,3-dimethylphenoxy group,

[0076] 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group,

[0077] 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group,

[0078] 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy

[0079] group, 2-tert-butyl-4-methylphenoxy group,

[0080] 2-tert-butyl-5-methylphenoxy group,

[0081] 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group,2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group,2,4,5-trimethylphenoxygroup, 2,4,6-trimethylphenoxy group,2-tert-butyl-3,4-dimethylphenoxy group,

[0082] 2-tert-butyl-3,5-dimethylphenoxy group,

[0083] 2-tert-butyl-3,6-dimethylphenoxy group,

[0084] 2,6-di-tert-butyl-3-methylphenoxy group,

[0085] 2-tert-butyl-4,5-dimethylphenoxy group,

[0086] 2,6-di-tert-butyl-4-methylphenoxy group,

[0087] 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group,2-tert-butyl-3,4,5-trimethylphenoxy group,

[0088] 2,3,4,6-tetramethylphenoxy group,

[0089] 2-tert-butyl-3,4,6-trimethylphenoxy group,

[0090] 2,6-di-tert-butyl-3,4-dimethylphenoxy group,

[0091] 2,3,5,6-tetramethylphenoxy group,

[0092] 2-tert-butyl-3,5,6-trimethylphenoxy group,

[0093] 2,6-di-tert-butyl-3,5-dimethylphenoxy group,

[0094] pentamethylphenoxy group, ethylphenoxy group,

[0095] n-propylphenoxy group, isopropylphenoxy group,

[0096] n-butylphenoxy group, sec-butylphenyl group,

[0097] tert-butylphenoxy group, n-hexylphenoxy group,

[0098] n-octylphenoxy group, n-decylphenoxy group,

[0099] n-tetradecylphenoxy group, naphthoxy group, anthracenoxy groupand the like.

[0100] Any of these aryloxy groups may also be partially substitutedwith a halogen atom such as a fluorine atom, chlorine atom, bromineatom, iodine atom and the like, an alkoxy group such as a methoxy group,ethoxy group and the like, an aryloxy group such as aphenoxy group andthe like, an aralkyloxy group such as a benzyloxy group and the like,etc.

[0101] As the di-substituted amino group represented by X in the generalformula (1), an amino group substituted with two hydrocarbon groups orsilyl groups is preferable, and examples of the hydrocarbon groupinclude alkyl groups having 1 to 10 carbon atoms such as a methyl group,ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butylgroup, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group,cyclohexyl group and the like, aryl groups having 6 to 10 carbon atomssuch as a phenyl group and the like, and aralkyl groups having 7 to 10carbon atoms such as a benzyl group and the like, etc. and examples ofthe silyl group include a trimethylsilyl group, tert-butyldimethylsilylgroup and the like. Examples of such di-substituted amino group includea dimethylamino group, diethylamino group, di-n-propylamino group,diisopropylamino group, di-n-butylamino group, di-sec-butylamino group,di-tert-butylamino group, diiosobutylamino group,tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylaminogroup, diphenylamino group, bistrimethylsilylamino group,bis-tert-butyldimethylsilylamino group and the like, and preferable area dimethylamino group, diethylamino group, diisopropylamino group,di-tert-butylamino group and bistrimethylsilylamino group.

[0102] Any of these di-substituted amino groups may also be partiallysubstituted with a halogen atom such as a fluorine atom, chlorine atom,bromine atom, iodine atom and the like, an alkoxy group such as amethoxy group, ethoxy group and the like, an aryloxy group such as aphenoxy group and the like, an aralkyloxy group such as a benzyloxygroup and the like, etc.

[0103] R¹ in the general formula (1) is preferably the alkyl group orsubstituted silyl group, and a methyl group, tert-butyl group ortrimethylsilyl group is more preferable.

[0104] Two Xs in the general formula (1) may mutually bond to form aring. As X, the halogen atom, alkyl group, alkoxy group or alkenediylgroup is preferable, and a chlorine atom, methyl group, methoxy group,3-hexene-2,5-diyl group or 1,4-diphenyl-2-butene-1,4-diyl group isfurther preferable.

[0105] As the multidentate mono-anionic ligand represented by A in thegeneral formula (1), for example, a cyclopentadienyl group, substitutedcyclopentadienyl group, indenyl group, substituted indenyl group,fluorenyl group, substituted fluorenyl group, tris(pyrazolyl) borategroup, tris(substituted pyrazolyl) borate group and the like are listed,and preferable are a substituted cyclopentadienyl group, substitutedindenyl group and substituted fluorenyl group.

[0106] A is preferably a multidentate mono-anionic ligand of thefollowing general formula (2):

[0107] wherein Cp¹ represents a group having a cyclopentadiene typeanion skeleton; and G represents a substituent having 1 to 30non-hydrogen atoms binding between Cp¹ and E.

[0108] As the group having a cyclopentadiene-type anion skeletonrepresented by Cp¹ in the above-mentioned general formula (2), there arelisted, for example, an η

[0109]⁵-cyclopentadienyl group, η⁵-methylcyclopentadienyl group,

[0110] η⁵-dimethylcyclopentadienyl group, η

[0111]⁵-trimethylcyclopentadienyl group, 72

[0112]⁵-tetramethylcyclopentadienyl group, η

[0113]⁵-ethylcyclopentadienyl group, η⁵-n-propylcyclopentadienyl group,η⁵-isopropylcyclopentadienyl group, η

[0114]⁵-n-butylcyclopentadienyl group, η

[0115]⁵-sec-butylcyclopentadienyl group, η

[0116]⁵-tert-butylcyclopentadienyl group, η

[0117]⁵-n-pentylcyclopentadienyl group, η

[0118]⁵-neopentylcyclopentadienyl group, η

[0119]⁵-n-hexylcyclopentadienyl group, η

[0120]⁵-n-octylcyclopentadienyl group, η⁵-phenylcyclopentadienyl group,η⁵-naphthylcyclopentadienyl group, η

[0121]⁵-trimethylsilylcyclopentadienyl group, η

[0122]⁵-triethylsilylcyclopentadienyl group, η

[0123]⁵-tert-butyldimethylsilylcyclopentadienyl group, η

[0124]⁵-indenyl group, η⁵-methylindenyl group, η⁵-dimethylindenyl group,η⁵-ethylindenyl group, η⁵-n-propylindenyl group, η

[0125]⁵-isopropylindenyl group, η⁵-n-butylindenyl group, η

[0126]⁵-sec-butylindenyl group, η⁵-tert-butylindenyl group, η

[0127]⁵-n-pentylindenyl group, η⁵-neopentylindenyl group, η

[0128]⁵-n-hexylindenyl group, η⁵-n-octylindenyl group, η

[0129]⁵-n-decylindenyl group, η⁵-phenylindenyl group, η

[0130]⁵-methylphenylindenyl group, η⁵-naphthylindenyl group, η

[0131]⁵-trimethylsilylindenyl group, η⁵-triethylsilylindenyl group,η⁵-tert-butyldimethylsilylindenyl group, η

[0132]⁵-tetrahydroindenyl group, η⁵-fluorenyl group, η

[0133]⁵-ethylfluorenyl group, η⁵-dimethylfluorenyl group, η

[0134]⁵-ethylfluorenyl group, η⁵-diethylfluorenyl group, η

[0135]⁵-n-propylfluorenyl group, η⁵-di-n-propylfluorenyl group, η

[0136]⁵-isopropylfluorenyl group, η⁵-diisopropylfluorenyl group,

[0137]⁵-n-butylfluorenyl group, η⁵-sec-butylfluorenyl group, η

[0138]⁵-tert-butylfluorenyl group, η⁵-di-n-butylfluorenyl group,

[0139] η⁵-di-sec-butylfluorenyl group, η⁵-di-tert-butylfluorenyl group,η⁵-n-pentylfluorenyl group, η⁵-neopentylfluorenyl group,η⁵-n-hexylfluorenyl group, η⁵-n-octylfluorenyl group,

[0140] η⁵-n-decylfluorenyl group, η⁵-n-dodecylfluorenyl group, η

[0141]⁵-phenylfluorenyl group, η⁵-di-phenylfluorenyl group, η

[0142]⁵-methylphenylfluorenyl group, η⁵-naphthylfluorenyl group,

[0143] η⁵-trimethylsilylfluorenyl group, η

[0144]⁵-bis-trimethylsilylfluorenyl group, η

[0145]⁵-triethylsilylfluorenyl group, η

[0146]⁵-tert-butyldimethylsilylfluorenyl group and the like, andpreferable are a η⁵-cyclopentadienyl group, η

[0147]⁵-methylcyclopentadienyl group, η

[0148]⁵-tert-butylcyclopentadienyl group, η

[0149]⁵-tetramethylcyclopentadienyl group, η⁵-indenyl group and

[0150] η⁵-fluorenyl group.

[0151] G in the general formula (2) represents a substituent having 1 to30 non-hydrogen atoms binding Cp¹ with E, and examples thereof include amethylene group; polymethylene groups such as a 1,2-ethylene group,1,3-propylene group and the like; cycloalkanediyl group;silicon-containing hydrocarbon groups such as a dialkylsilylene group,silacycloalkanedilyl group and the like; germanium-containinghydrocarbon groups such as a dialkylgermylene group,germylacycloalkanediyl group and the like; atoms of XVI group in theperiodic table such as an oxygen atom and sulfur atom; substitutedphenylene and the like, and in some cases, a substituent combining themmay also be permissible, and preferable are a polymethylene group,substituted phenylene group, substituted phenyleneoxy group, substitutedphenylenethio group and groups of the following general formula (4), andparticularly preferable are groups of the following general formula (4):

[0152] (wherein, J represents an atom of XIV group in the periodic tableof element; each of R² and R³ independently represents a hydrogen atom,halogen atom, alkyl group, aralkyl group, aryl group, substituted silylgroup, alkoxy group, aralkyloxy group, aryloxy group or di-substitutedamino group, and a plurality of R²s may bond mutually to form a ring; mrepresents an integer of from 0 to 4).

[0153] Namely, the transition metal compound of the above-mentionedgeneral formula (1) is preferably a transition metal compound of thefollowing general formula (3):

[0154] (wherein, M represents a titanium atom, zirconium atom or hafniumatom in the +3 formal oxide condition; Cp¹ represents a group having acyclopentadiene-type anion skeleton; J represents an atom of XIV groupin the periodic table of element; each of R² and R³ independentlyrepresents a hydrogen atom, halogen atom, alkyl group, aralkyl group,aryl group, substituted silyl group, alkoxy group, aralkyloxy group,aryloxy group or di-substituted amino group, and a plurality of R²s maybond mutually to form a ring; m represents an integer of from 0 to 4; Erepresents an oxygen atom or sulfur atom; R¹ represents an alkyl group,aralkyl group, aryl group or substituted silyl group; each of two Xsindependently represents a hydrogen atom, halogen atom, alkyl group,aralkyl group, aryl group, substituted silyl group, alkoxy group,aralkyloxy group, aryloxy group or di-substituted amino group, and twoXs may bond mutually to form a ring; D represents a neutral ligandcoordinated on M; and n represents an integer of from 0 to 2.).

[0155] In the above-mentioned general formula (3), J represents an atomof XIV group in the periodic table of element, and as specific examplesthereof, a carbon atom, silicon atom, germanium atom and the like arelisted, and a carbon atom or a silicon atom is preferable.

[0156] In the general formula (3), M, D, n, X and Cp¹ are as definedpreviously in the above-mentioned general formula (1) or (2).

[0157] The halogen atom, alkyl group, aralkyl group, aryl group,substituted silyl group, alkoxy group, aralkyloxy group, aryloxy groupand di-substituted amino group represented by R² and R³ in the generalformula (3) are as defined for X in the general formula (1). mrepresents an integer of from 0 to 4 indicating the number ofsubstituent R² on a benzene ring, preferably an integer of from 0 to 2,and R² in this case is preferably an alkyl group, alkoxy group orsubstituted silyl group, more preferably an alkyl group. Each of R³sindependently represents an alkyl group, alkoxy group, aryl group oraryloxy group, or cycloalkanediyl group or silacycloalkanediyl groupobtained by combining two R³ and J, further preferably, a methyl group,ethyl group, methoxy group, ethoxy group or phenyl group.

[0158] Specific examples of the transition metal compound of theabove-mentioned general formula (1) include

[0159] (methoxycyclopentadienyl)titanium dichloride,

[0160] (ethoxycyclopentadienyl)titanium dichloride,

[0161] (n-propoxycyclopentadienyl)titanium dichloride,

[0162] (isopropoxycyclopentadienyl)titanium dichloride,

[0163] (n-butoxycyclopentadienyl)titanium dichloride,

[0164] (t-butoxycyclopentadienyl)titanium dichloride,

[0165] (trimethylsiloxycyclopentadienyl)titanium dichloride,

[0166] [(methoxymethyl)cyclopentadienyl]titanium dichloride,

[0167] [(ethoxymethyl)cyclopentadienyl]titanium dichloride,

[0168] [(n-propoxymethyl)cyclopentadienyl]titanium dichloride,

[0169] [(isopropoxymethyl)cyclopentadienyl]titanium dichloride,

[0170] [(n-butoxymethyl)cyclopentadienyl]titanium dichloride,

[0171] [(t-butoxymethyl)cyclopentadienyl]titanium dichloride,

[0172] [(trimethylsiloxymethyl)cyclopentadienyl]titanium dichloride,[(methoxyethyl)cyclopentadienyl]titanium dichloride,[(ethoxyethyl)cyclopentadienyl]titanium dichloride,[(n-propoxyethyl)cyclopentadienyl]titanium dichloride,[(isopropoxyethyl)cyclopentadienyl]titanium dichloride,[(n-butoxyethyl)cyclopentadienyl]titanium dichloride,[(t-butoxyethyl)cyclopentadienyl]titanium dichloride,

[0173] [(trimethylsiloxyethyl)cyclopentadienyl]titanium dichloride,[(methoxy-n-propyl)cyclopentadienyl]titanium dichloride,[(ethoxy-n-propyl)cyclopentadienyl]titanium dichloride,

[0174] [(n-propoxy-n-propyl)cyclopentadienyl]titanium dichloride,

[0175] [(isopropoxy-n-propyl)cyclopentadienyl]titanium dichloride,[(n-butoxy-n-propyl)cyclopentadienyl]titanium dichloride,[(t-butoxy-n-propyl)cyclopentadienyl]titanium dichloride,

[0176] [(trimethylsiloxy-n-propyl)cyclopentadienyl]titanium dichloride,

[0177] [(methoxydimethylsilyl)cyclopentadienyl]titanium dichloride,

[0178] [(ethoxydimethylsilyl)cyclopentadienyl]titanium dichloride,

[0179] [(n-propoxydimethylsilyl)cyclopentadienyl]titanium dichloride,

[0180] [(isopropoxydimethylsilyl)cyclopentadienyl]titanium dichloride,

[0181] [(n-butoxydimethylsilyl)cyclopentadienyl]titanium dichloride,

[0182] [(t-butoxydimethylsilyl)cyclopentadienyl]titanium dichloride,

[0183] [(trimethylsiloxydimethylsilyl)cyclopentadienyl]titaniumdichloride,

[0184] [(methoxydimethylsilylmethyl)cyclopentadienyl]titaniumdichloride,

[0185] [(ethoxydimethylsilylmethyl)cyclopentadienyl]titanium dichloride,

[0186] [(n-propoxydimethylsilylmethyl)cyclopentadienyl]titaniumdichloride,

[0187] [(isopropoxydimethylsilylmethyl)cyclopentadienyl]titaniumdichloride,

[0188] [(n-butoxydimethylsilylmethyl)cyclopentadienyl]titaniumdichloride,

[0189] [(t-butoxydimethylsilylmethyl)cyclopentadienyl]titaniumdichloride,

[0190] [(trimethylsiloxydimethylsilylmethyl)cyclopentadienyl]titaniumdichloride,

[0191] [(methoxydimethylsilylethyl)cyclopentadienyl]titanium dichloride,

[0192] [(ethoxydimethylsilylethyl)cyclopentadienyl]titanium dichloride,

[0193] [(n-propoxydimethylsilylethyl)cyclopentadienyl]titaniumdichloride,

[0194] [(isopropoxydimethylsilylethyl)cyclopentadienyl]titaniumdichloride,

[0195] [(n-butoxydimethylsilylethyl)cyclopentadienyl]titaniumdichloride,

[0196] [(t-butoxydimethylsilylethyl)cyclopentadienyl]titaniumdichloride,

[0197] [(trimethylsiloxydimethylsilylethyl)cyclopentadienyl]titaniumdichloride,

[0198] [(methoxydimethylsilyl-n-propyl)cyclopentadienyl]titaniumdichloride,

[0199] [(ethoxydimethylsilyl-n-propyl)cyclopentadienyl]titaniumdichloride,

[0200] [(n-propoxydimethylsilyl-n-propyl)cyclopentadienyl]titaniumdichloride,

[0201] [(isopropoxydimethylsilyl-n-propyl)cyclopentadienyl]titaniumdichloride,

[0202] [(n-butoxydimethylsilyl-n-propyl)cyclopentadienyl]titaniumdichloride,

[0203] [(t-butoxydimethylsilyl-n-propyl)cyclopentadienyl]titaniumdichloride,

[0204] [(trimethylsiloxydimethylsilyl-n-propyl)cyclopentadienyl]titaniumdichloride,

[0205] [(methoxyphenyl)cyclopentadienyl]titanium dichloride,

[0206] [(ethoxyphenyl)cyclopentadienyl]titanium dichloride,

[0207] [(n-propoxyphenyl)cyclopentadienyl]titanium dichloride,

[0208] [(isopropoxyphenyl)cyclopentadienyl]titanium dichloride,

[0209] [(n-butoxyphenyl)cyclopentadienyl]titanium dichloride,

[0210] [(t-butoxyphenyl)cyclopentadienyl]titanium dichloride,

[0211] [(trimethylsiloxyphenyl)cyclopentadienyl]titanium dichloride,

[0212] [(methoxyphenylmethyl)cyclopentadienyl]titanium dichloride,

[0213] [(ethoxyphenylmethyl)cyclopentadienyl]titanium dichloride,

[0214] [(n-propoxyphenylmethyl)cyclopentadienyl]titanium dichloride,

[0215] [(isopropoxyphenylmethyl)cyclopentadienyl]titanium dichloride,

[0216] [(n-butoxyphenylmethyl)cyclopentadienyl]titanium dichloride,

[0217] [(t-butoxyphenylmethyl)cyclopentadienyl]titanium dichloride,

[0218] [(trimethylsiloxyphenylmethyl)cyclopentadienyl]titaniumdichloride,

[0219] [(methoxyphenylethyl)cyclopentadienyl]titanium dichloride,

[0220] [(ethoxyphenylethyl)cyclopentadienyl]titanium dichloride,

[0221] [(n-propoxyphenylethyl)cyclopentadienyl]titanium dichloride,

[0222] [(isopropoxyphenylethyl)cyclopentadienyl]titanium dichloride,

[0223] [(n-butoxyphenylethyl)cyclopentadienyl]titanium dichloride,

[0224] [(t-butoxyphenylethyl)cyclopentadienyl]titanium dichloride,

[0225] [(trimethylsiloxyphenylethyl)cyclopentadienyl]titaniumdichloride,

[0226] [(methoxyphenyl-n-propyl)cyclopentadienyl]titanium dichloride,

[0227] [(ethoxyphenyl-n-propyl)cyclopentadienyl]titanium dichloride,

[0228] [(n-propoxyphenyl-n-propyl)cyclopentadienyl]titanium dichloride,

[0229] [(isopropoxyphenyl-n-propyl)cyclopentadienyl]titanium dichloride,

[0230] [(n-butoxyphenyl-n-propyl)cyclopentadienyl]titanium dichloride,

[0231] [(t-butoxyphenyl-n-propyl)cyclopentadienyl]titanium dichloride,

[0232] [(trimethylsiloxyphenyl-n-propyl)cyclopentadienyl]titaniumdichloride,

[0233] {[dimethyl(methoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0234] {[dimethyl(ethoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0235] {[dimethyl(n-propoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0236] {[dimethyl(isopropoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0237] {[dimethyl(n-butoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0238] {[dimethyl(t-butoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0239] {[dimethyl(trimethylsiloxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0240] {[dimethyl(methoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0241] {[dimethyl(ethoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0242] {[dimethyl(n-propoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0243] {[dimethyl(isopropoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0244] {[dimethyl(n-butoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0245] {[dimethyl(t-butoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0246] {[dimethyl(trimethylsiloxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0247] {[(6-methyl-1-methoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0248] {[(1-ethoxy-6-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0249] {[(6-methyl-1-n-propoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0250] {[(6-methyl-1-isopropoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0251] {[(1-n-butoxy-6-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0252] {[(1-t-butoxy-6-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0253]{[(6-methy-1-trimethylsiloxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0254] {[dimethyl(6-methy-1-methoxyphenyl)methyl]cyclopentadieny1}titanium dichloride,

[0255] {[dimethyl(1-ethoxy-6-methylphenyl)methyl]cyclopentadieny1}titanium dichloride,

[0256]{[dimethyl(6-methyl-1-n-propoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0257]{[dimethyl(6-methyl-1-isopropoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0258]{[dimethyl(1-n-butoxy-6-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0259]{[dimethyl(1-t-butoxy-6-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0260]{[dimethyl(6-methyl-1-trimethylsiloxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0261]{[dimethyl(6-methyl-1-methoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0262]{[dimethyl(1-ethoxy-6-methylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0263]{[dimethyl(6-methyl-1-n-propoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0264]{[dimethyl(6-methyl-1-isopropoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0265]{[dimethyl(1-n-butoxy-6-methylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0266]{[dimethyl(1-t-butoxy-6-methylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0267]{[dimethyl(6-methyl-1-trimethylsiloxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0268] {[(4,6-dimethyl-1-methoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0269] {[(1-ethoxy-4,6-dimethylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0270]{[(4,6-dimethyl-1-n-propoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0271]{[(4,6-dimethyl-1-isopropoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0272] {[(1-n-butoxy-4,6-dimethylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0273] {[(1-t-butoxy-4,6-dimethylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0274]{[(4,6-dimethyl-1-trimethylsiloxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0275]{[dimethyl(4,6-dimethyl-1-methoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0276]{[dimethyl(1-ethoxy-4,6-dimethylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0277]{[dimethyl(4,6-dimethyl-1-n-propoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0278]{[dimethyl(4,6-dimethyl-1-isopropoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0279]{[dimethyl(1-n-butoxy-4,6-dimethylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0280]{[dimethyl(1-t-butoxy-4,6-dimethylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0281]{[dimethyl(4,6-dimethyl-1-trimethylsiloxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0282]{[dimethyl(4,6-dimethyl-1-methoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0283]{[dimethyl(1-ethoxy-4,6-dimethylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0284]{[dimethyl(4,6-dimethyl-1-n-propoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0285]{[dimethyl(4,6-dimethyl-1-isopropoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0286]{[dimethyl(1-n-butoxy-4,6-dimethylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0287]{[dimethyl(1-t-butoxy-4,6-dimethylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0288]{[dimethyl(4,6-dimethyl-1-trimethylsiloxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0289] {[(6-t-butyl-1-methoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0290] {[(6-t-butyl-1-ethoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0291] {[(6-t-butyl-1-n-propoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0292] {[(6-t-butyl-1-isopropoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0293] {[(6-t-butyl-1-n-butoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0294] {[(1-t-butoxy-6-t-butylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0295]{[(6-t-butyl-1-trimethylsiloxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0296]{[dimethyl(6-t-butyl-1-methoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0297]{[dimethyl(6-t-butyl-1-ethoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0298]{[dimethyl(6-t-butyl-1-n-propoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0299]{[dimethyl(6-t-butyl-1-isopropoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0300]{[dimethyl(6-t-butyl-1-n-butoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0301]{[dimethyl(1-t-butoxy-6-t-butylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0302]{[dimethyl(6-t-butyl-1-trimethylsiloxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0303]{[dimethyl(6-t-butyl-1-methoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0304]{[dimethyl(6-t-butyl-1-ethoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0305]{[dimethyl(6-t-butyl-1-n-propoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0306]{[dimethyl(6-t-butyl-1-isopropoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0307]{[dimethyl(6-t-butyl-1-n-butoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0308]{[dimethyl(1-t-butoxy-6-t-butylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0309]{[dimethyl(6-t-butyl-1-trimethylsiloxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0310]{[(4,6-di-t-butyl-1-methoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0311] {[(4,6-di-t-butyl-1-ethoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0312]{[(4,6-di-t-butyl-1-n-propoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0313]{[(4,6-di-t-butyl-1-isopropoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0314]{[(4,6-di-t-butyl-1-n-butoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0315]{[(1-t-butoxy-4,6-di-t-butylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0316]{[(4,6-di-t-butyl-1-trimethylsiloxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0317]{[dimethyl(4,6-di-t-butyl-1-methoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0318]{[dimethyl(4,6-di-t-butyl-1-ethoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0319]{[dimethyl(4,6-di-t-butyl-1-n-propoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0320]{[dimethyl(4,6-di-t-butyl-1-isopropoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0321]{[dimethyl(4,6-di-t-butyl-1-n-butoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0322]{[dimethyl(1-t-butoxy-4,6-di-t-butylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0323]{[dimethyl(4,6-di-t-butyl-1-trimethylsiloxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0324]{[dimethyl(4,6-di-t-butyl-1-methoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0325]{[dimethyl(4,6-di-t-butyl-1-ethoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0326]{[dimethyl(4,6-di-t-butyl-1-n-propoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0327]{[dimethyl(4,6-di-t-butyl-1-isopropoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0328]{[dimethyl(4,6-di-t-butyl-1-n-butoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0329]{[dimethyl(1-t-butoxy-4,6-di-t-butylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0330]{[dimethyl(4,6-di-t-butyl-1-trimethylsiloxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0331]{[(6-t-butyl-4-methyl-1-methoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0332]{[(6-t-butyl-1-ethoxy-4-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0333]{[(6-t-butyl-4-methyl-1-n-propoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0334]{[(6-t-butyl-4-methyl-1-isopropoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0335]{[(1-n-butoxy-6-t-butyl-4-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0336]{[(1-t-butoxy-6-t-butyl-4-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0337]{[(6-t-butyl-4-methyl-1-trimethylsiloxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0338]{[dimethyl(6-t-butyl-4-methyl-1-methoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0339]{[dimethyl(6-t-butyl-1-ethoxy-4-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0340]{[dimethyl(6-t-butyl-4-methyl-1-n-propoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0341]{[dimethyl(6-t-butyl-4-methyl-1-isopropoxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0342]{[dimethyl(1-n-butoxy-6-t-butyl-4-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0343]{[dimethyl(1-t-butoxy-6-t-butyl-4-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0344]{[dimethyl(6-t-butyl-4-methyl-1-trimethylsiloxyphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0345]{[dimethyl(6-t-butyl-4-methyl-1-methoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0346]{[dimethyl(6-t-butyl-1-ethoxy-4-methylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0347]{[dimethyl(6-t-butyl-4-methyl-1-n-propoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0348]{[dimethyl(6-t-butyl-4-methyl-1-isopropoxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0349]{[dimethyl(1-n-butoxy-6-t-butyl-4-methylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0350]{[dimethyl(1-t-butoxy-6-t-butyl-4-methylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0351]{[dimethyl(6-t-butyl-4-methyl-1-trimethylsiloxyphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0352] (methylthiocyclopentadienyl)titanium dichloride,

[0353] (ethylthiocyclopentadienyl)titanium dichloride,

[0354] (n-propylthiocyclopentadienyl)titanium dichloride,

[0355] (isopropylthiocyclopentadienyl)titanium dichloride,

[0356] (n-butylthiocyclopentadienyl)titanium dichloride,

[0357] (t-butylthiocyclopentadienyl)titanium dichloride,

[0358] [(methylthiomethyl)cyclopentadienyl]titanium dichloride,

[0359] [(ethylthiomethyl)cyclopentadienyl]titanium dichloride,

[0360] [(n-propylthiomethyl)cyclopentadienyl]titanium dichloride,

[0361] [(isopropylthiomethyl)cyclopentadienyl]titanium dichloride,[(n-butylthiomethyl)cyclopentadienyl]titanium dichloride,[(t-butylthiomethyl)cyclopentadienyl]titanium dichloride,[(methylthioethyl)cyclopentadienyl]titanium dichloride,[(ethylthioethyl)cyclopentadienyl]titanium dichloride,[(n-propylthioethyl)cyclopentadienyl]titanium dichloride,

[0362] [(isopropylthioethyl)cyclopentadienyl]titanium dichloride,

[0363] [(n-butylthioethyl)cyclopentadienyl](titanium dichoride,

[0364] [(t-butylthioethyl)cyclopentadienyl]titanium dichloride,

[0365] [(methylthio-n-propyl)cyclopentadienyl]titanium dichloride,

[0366] [(ethylthio-n-propyl)cyclopentadienyl]titanium dichloride,

[0367] [(n-propylthio-n-propyl)cyclopentadienyl]titanium

[0368] [(isopropylthio-n-propyl)cyclopentadienyl]titanium dichloride,

[0369] [(n-butylthio-n-propyl)cyclopentadienyl]titanium dichloride,

[0370] [(t-butylthio-n-propyl)cyclopentadienyl]titanium dichloride,

[0371] {[dimethyl(methylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0372] {[dimethyl(ethylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0373] {[dimethyl(n-propylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0374] {[dimethyl(isopropylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0375] {[dimethyl(n-butylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0376] {[dimethyl(t-butylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0377]{[dimethyl(trimethylsilylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0378] {[dimethyl(methylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0379] {[dimethyl(ethylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0380] {[dimethyl(n-propylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0381] {[dimethyl(isopropylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0382] {[dimethyl(n-butylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0383] {[dimethyl(t-butylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0384]{[dimethyl(trimethylsilylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0385] {[(6-methyl-1-methylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0386] {[(1-ethylthio-6-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0387] {[(6-methyl-1-n-propylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0388]{[(6-methyl-1-isopropylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0389] {[(1-n-butylthio-6-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0390] {[(1-t-butylthio-6-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0391]{[(6-methyl-1-trimethylsilylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0392]{[dimethyl(6-methyl-1-methylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0393]{[dimethyl(1-ethylthio-6-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0394]{[dimethyl(6-methyl-1-n-propylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0395]{[dimethyl(6-methyl-1-isopropylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0396]{[dimethyl(1-n-butylthio-6-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0397]{[dimethyl(1-t-butylthio-6-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0398]{[dimethyl(6-methyl-1-trimethylsilylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0399]{[dimethyl(6-methyl-1-methylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0400]{[dimethyl(1-ethylthio-6-methylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0401]{[dimethyl(6-methyl-1-n-propylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0402]{[dimethyl(6-methyl-1-isopropylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0403]{[dimethyl(1-n-butylthio-6-methylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0404]{[dimethyl(1-t-butylthio-6-methylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0405]{[dimethyl(6-methyl-1-trimethylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0406]{[(4,6-dimethyl-1-methylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0407]{[(1-ethylthio-4,6-dimethylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0408]{[(4,6-dimethyl-1-n-propylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0409]{[(4,6-dimethyl-1-isopropylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0410]{[(1-n-butylthio-4,6-dimethylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0411]{[(1-t-butylthio-4,6-dimethylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0412]{[(4,6-dimethyl-1-trimethylsilylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0413]{[dimethyl(4,6-dimethyl-1-methylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0414]{[dimethyl(1-ethylthio-4,6-dimethylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0415]{[dimethyl(4,6-dimethyl-1-n-propylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0416]{[dimethyl(4,6-dimethyl-1-isopropylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0417]{[dimethyl(1-n-butylthio-4,6-dimethylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0418]{[dimethyl(1-t-butylthio-4,6-dimethylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0419]{[dimethyl(4,6-dimethyl-1-trimethylsilylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0420]{[dimethyl(4,6-dimethyl-1-methylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0421]{[dimethyl(1-ethylthio-4,6-dimethylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0422]{[dimethyl(4,6-dimethyl-1-n-propylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0423]{[dimethyl(4,6-dimethyl-1-isopropylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0424]{[dimethyl(1-n-butylthio-4,6-dimethylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0425]{[dimethyl(1-t-butylthio-4,6-dimethylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0426]{[dimethyl(4,6-dimethyl-1-trimethylsilylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0427] {[(6-t-butyl-1-methylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0428] {[(6-t-butyl-1-ethylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0429]{[(6-t-butyl-1-n-propylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0430]{[(6-t-butyl-1-isopropylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0431] {[(6-t-butyl-1-n-butylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0432] {[(1-t-butylthio-6-t-butylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0433]{[(6-t-butyl-1-trimethylsilylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0434]{[dimethyl(6-t-butyl-1-methylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0435]{[dimethyl(6-t-butyl-1-ethylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0436]{[dimethyl(6-t-butyl-1-n-propylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0437]{[dimethyl(6-t-butyl-1-isopropylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0438]{[dimethyl(6-t-butyl-1-n-butylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0439]{[dimethyl(1-t-butylthio-6-t-butylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0440]{[dimethyl(6-t-butyl-1-trimethylsilylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0441]{[dimethyl(6-t-butyl-1-methylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0442]{[dimethyl(6-t-butyl-1-ethylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0443]{[dimethyl(6-t-butyl-1-n-propylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0444]{[dimethyl(6-t-butyl-1-isopropylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0445]{[dimethyl(6-t-butyl-1-n-butylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0446]{[dimethyl(1-t-butylthio-6-t-butylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0447]{[dimethyl(6-t-butyl-1-trimethylsilylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0448]{[(4,6-di-t-butyl-1-methylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0449]{[(4,6-di-t-butyl-1-ethylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0450]{[(4,6-di-t-butyl-1-n-propylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0451]{[(4,6-di-t-butyl-1-isopropylthiophenyl)methyl]cyclopentacdienyl}titaniumdichloride,

[0452]{[(4,6-di-t-butyl-1-n-butylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0453]{[(1-t-butylthio-4,6-di-t-butylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0454]{[(4,6-di-t-butyl-1-trimethylsilylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0455]{[dimethyl(4,6-di-t-butyl-1-methylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0456]{[dimethyl(4,6-di-t-butyl-1-ethylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0457]{[dimethyl(4,6-di-t-butyl-1-n-propylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0458]{[dimethyl(4,6-di-t-butyl-1-isopropylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0459]{[dimethyl(4,6-di-t-butyl-1-n-butylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0460]{[dimethyl(1-t-butylthio-4,6-di-t-butylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0461]{[dimethyl(4,6-di-t-butyl-1-trimethylsilylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0462]{[dimethyl(4,6-di-t-butyl-1-trimethylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0463]{[dimethyl(4,6-di-t-butyl-1-ethylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0464]{[dimethyl(4,6-di-t-butyl-1-n-propylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0465]{[dimethyl(4,6-di-t-butyl-1-isopropylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0466]{[dimethyl(4,6-di-t-butyl-1-n-butylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0467]{[dimethyl(1-t-butylthio-4,6-di-t-butylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0468]{[dimethyl(4,6-di-t-butyl-i-trimethylsilylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0469]{[(6-t-butyl-4-methyl-1-methylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0470]{[(6-t-butyl-1-ethylthio-4-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0471]{[(6-t-butyl-4-methyl-1-n-propylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0472]{[(6-t-butyl-4-methyl-1-isopropylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0473]{[(1-n-butylthio-6-t-butyl-4-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0474]{[(1-t-butylthio-6-t-butyl-4-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0475]{[(6-t-butyl-4-methyl-1-trimethylsilylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0476]{[dimethyl(6-t-butyl-4-methyl-1-methylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0477]{[dimethyl(6-t-butyl-1-ethylthio-4-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0478]{[dimethyl(6-t-butyl-4-methyl-1-n-propylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0479]{[dimethyl(6-t-butyl-4-methyl-1-isopropylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0480]{[dimethyl(1-n-butylthio-6-t-butyl-4-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0481]{[dimethyl(1-t-butylthio-6-t-butyl-4-methylphenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0482]{[dimethyl(6-t-butyl-4-methyl-1-trimethylsilylthiophenyl)methyl]cyclopentadienyl}titaniumdichloride,

[0483]{[dimethyl(6-t-butyl-4-methyl-1-methylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0484]{[dimethyl(6-t-butyl-1-ethylthio-4-methylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0485]{[dimethyl(6-t-butyl-4-methyl-1-n-propylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0486]{[dimethyl(6-t-butyl-4-methyl-1-isopropylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0487]{[dimethyl(1-n-butylthio-6-t-butyl-4-methylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0488]{[dimethyl(1-t-butylthio-6-t-butyl-4-methylphenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0489]{[dimethyl(6-t-butyl-4-methyl-1-trimethylsilylthiophenyl)silyl]cyclopentadienyl}titaniumdichloride,

[0490] [(methoxyphenylthio)cyclopentadienyl]titanium dichloride,

[0491] [(ethoxyphenylthio)cyclopentadienyl]titanium dichloride,

[0492] [(n-propoxyphenylthio)cyclopentadienyl]titanium dichloride,

[0493] [(isopropoxyphenylthio)cyclopentadienyl]titanium dichloride,

[0494] [(n-butoxyphenylthio)cyclopentadienyl]titanium dichloride,

[0495] [(t-butoxyphenylthio)cyclopentadienyl]titanium dichloride,

[0496] [(trimethylsiloxyphenylthio)cyclopentadienyl]titanium dichloride,

[0497] [(6-methyl-1-methoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0498] [(1-ethoxy-6-methylthio)cyclopentadienyl]titanium dichloride,

[0499] [(6-methyl-1-n-propoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0500] [(6-methyl-1-isopropoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0501] [(1-n-butoxy-6-methylphenylthio)cyclopentadienyl]titaniumdichloride,

[0502] [(1-t-butoxy-6-methylphenylthio)cyclopentadienyl]titaniumdichloride,

[0503] [(6-methyl-1-trimethylsiloxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0504] [(4,6-dimethyl-1-methoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0505] [(1-ethoxy-4,6-dimethylphenylthio)cyclopentadienyl]titaniumdichloride,

[0506] [(4,6-dimethyl-1-n-propoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0507] [(4,6-dimethyl-1-isopropoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0508] [(1-n-butoxy-4,6-dimethylphenylthio)cyclopentadienyl]titaniumdichloride,

[0509] [(1-t-butoxy-4,6-dimethylphenylthio)cyclopentadienyl]titaniumdichloride,

[0510][(4,6-dimethyl-1-trimethylsiloxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0511] [(6-t-butyl-1-methoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0512] [(6-t-butyl-1-ethoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0513] [(6-t-butyl-1-n-propoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0514] [(6-t-butyl-1-isopropoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0515] [(6-t-butyl-1-n-butoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0516] [(1-t-butoxy-6-t-butylphenylthio)cyclopentadienyl]titaniumdichloride,

[0517] [(6-t-butyl-1-trimethylsiloxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0518] [(4,6-di-t-butyl-1-methoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0519] [(4,6-di-t-butyl-1-ethoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0520] [(4,6-di-t-butyl-1-n-propoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0521] [(4,6-di-t-butyl-1-isopropoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0522] [(4,6-di-t-butyl-1-n-butoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0523] [(1-t-butoxy-4,6-di-t-butylphenylthio)cyclopentadienyl]titaniumdichloride,

[0524][(4,6-di-t-butyl-1-trimethylsiloxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0525][(6-t-butyl-4-methyl-1-methoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0526] [(6-t-butyl-1-ethoxy-4-methylphenylthio)cyclopentadienyl]titaniumdichloride,

[0527][(6-t-butyl-4-methyl-1-n-propoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0528][(6-t-butyl-4-methyl-1-isopropoxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0529][(1-n-butoxy-6-t-butyl-4-methylphenylthio)cyclopentadienyl]titaniumdichloride,

[0530][(1-t-butoxy-6-t-butyl-4-methylphenylthio)cyclopentadienyl]titaniumdichloride,

[0531][(6-t-butyl-4-methyl-1-trimethylsiloxyphenylthio)cyclopentadienyl]titaniumdichloride,

[0532] [(methoxyphenoxy)cyclopentadienyl]titanium dichloride,

[0533] [(ethoxyphenoxy)cyclopentadienyl]titanium dichloride,

[0534] [(n-propoxyphenoxy)cyclopentadienyl]titanium dichloride,

[0535] [(isopropoxyphenoxy)cyclopentadienyl]titanium dichloride,

[0536] [(n-butoxyphenoxy)cyclopentadienyl]titanium dichloride,

[0537] [(t-butoxyphenoxy)cyclopentadienyl]titanium dichloride,

[0538] [(trimethylsiloxyphenoxy)cyclopentadienyl]titanium dichloride,

[0539] [(6-methyl-1-methoxyphenoxy)cyclopentadienyl]titanium dichloride,

[0540] [(1-ethoxy-6-methylphenoxy)cyclopentadienyl]titanium dichloride,

[0541] [(6-methyl-1-n-propoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0542] [(6-methyl-1-isopropoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0543] [(1-n-butoxy-6-methylphenoxy)cyclopentadienyl]titaniumdichloride,

[0544] [(1-t-butoxy-6-methylphenoxy)cyclopentadienyl]titaniumdichloride,

[0545] [(6-methyl-1-trimethylsiloxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0546] [(4,6-dimethyl-1-methoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0547] [(1-ethoxy-4,6-dimethylphenoxy)cyclopentadienyl]titaniumdichloride,

[0548] [(4,6-dimethy-1-n-propoxylphenoxy)cyclopentadienyl]titaniumdichloride,

[0549] [(4,6-dimethy-1-isopropoxylphenoxy)cyclopentadienyl]titaniumdichloride,

[0550] [(1-n-butoxy-4,6-dimethylphenoxy)cyclopentadienyl]titaniumdichloride,

[0551] [(1-t-butoxy-4,6-dimethylphenoxy)cyclopentadienyl]titaniumdichloride,

[0552] [(4,6-dimethyl-1-trimethylsiloxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0553] [(6-t-butyl-1-methoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0554] [(6-t-butyl-1-ethoxyphenoxy)cyclopentadienyl]titanium dichloride,

[0555] [(6-t-butyl-1-n-propoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0556] [(6-t-butyl-1-isopropoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0557] [(6-t-butyl-1-n-butoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0558] [(1-t-butoxy-6-t-butylphenoxy)cyclopentadienyl]titaniumdichloride,

[0559] [(6-t-buyl-1-trimethylsiloxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0560] [(4,6-di-t-butyl-1-methoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0561] [(4,6-di-t-butyl-1-ethoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0562] [(4,6-di-t-butyl-1-n-propoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0563] [(4,6-di-t-butyl-1-isopropoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0564] [(4,6-di-t-butyl-1-n-butoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0565] [(1-t-butoxy-4,6-di-t-butylphenoxy)cyclopentadienyl]titaniumdichloride,

[0566][(4,6-di-t-butyl-1-trimethylsiloxyphenoxy)cyclopentadieny]titaniumdichloride,

[0567] [(6-t-butyl-4-methyl-1-methoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0568] [(6-t-butyl-1-ethoxy-4-methylphenoxy)cyclopentadienyl]titaniumdichloride,

[0569] [(6-t-butyl-4-methyl-1-n-propoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0570][(6-t-butyl-4-methyl-1-isopropoxyphenoxy)cyclopentadienyl]titaniumdichloride,

[0571] [(1-n-butoxy-6-t-butyl-4-methylphenoxy)cyclopentadienyl]titaniumdichloride,

[0572] [(1-t-butoxy-6-t-butyl-4-methylphenoxy)cyclopentadienyl]titaniumdichloride,

[0573][(6-t-butyl-4-methyl-1-trimethylsiloxyphenoxy)cyclopentadienyl]titaniumdichloride and the like, transition metal compounds obtained bysubstituting titanium in these compounds with zirconium or hafnium,transition metal compounds obtained by substituting chloride in thesecompounds with bromide, iodide, dimethylamide, diethylamide, n-butoxideor isopropoxide, transition metal compounds obtained by substitutingcyclopentadienyl in these compounds with dimethylcyclopentadienyl,trimethylcyclopentadienyl, tetramethylcyclopentadienyl,n-butylcyclopentadienyl, tert-butyldimethylsilylcyclopentadienyl,indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl.

[0574] The transition metal compound (A) of the present invention can beproduced by methods described below.

[0575] Ligands required in synthesis of the transition metal compoundcan be synthesized by methods disclosed in, for example, EP-A-0842939,Q. Huang, et al., Transition Metal. Chem. 1990, 15, 483, and the like.

[0576] And, the transition metal compound (A) can be obtained byreacting a metal salt obtained by reacting a ligand obtained by theabove-described method with an alkaline metal compound or alkaline earthmetal compound, with a compound of a trivalent transition metal of the4^(th) group of the Periodic Table of the Elements, or a mixture of acompound of a tetravalent transition metal of the 4^(th) group and areducing agent.

[0577] The catalyst for addition polymerization of the present inventionis a catalyst for addition polymerization obtained by allowing thetransition metal compound (A) to contact with a co-catalyst foractivation. The catalyst for addition polymerization of the presentinvention is preferably a catalyst for addition polymerization obtainedby allowing the transition metal compound (A) to contact with thefollowing (B) and/or the following (C):

[0578] (B): one or more aluminum compounds selected from the following(B1) to (B3):

[0579] (B1) organic aluminum compounds of the general formula E¹_(a)AlZ_(3-a),

[0580] (B2) cyclic aluminoxanes having a structure of the generalformula {—Al(E²)—O—}_(b),

[0581] (B3) linear aluminoxanes having a structure of the generalformula E³{—Al(E³)—O—}_(c)AlE³ ₂,

[0582] wherein, each of E¹, E² and E³ represents a hydrocarbon group,and all E¹s, all E²s or all E³s may be the same or different; Zrepresents a hydrogen atom or halogen atom and all Zs may be the same ordifferent; a represents a number satisfying O<a≦3, b represents aninteger of 2 or more; and c represents an integer of 1 or more,

[0583] (C) one or more boron compounds selected from the following (C1)to (C3):

[0584] (C1) boron compounds of the general formula BQ¹Q²Q³,

[0585] (C2) boron compounds of the general formula G⁺(BQ¹Q²Q³Q⁴)⁻,

[0586] (C3) boron compounds of the general formula (L-H)⁺(BQ¹Q²Q³Q⁴)⁻,

[0587] wherein B represents a trivalent boron atom; Q¹ to Q⁴ represent ahalogen atom, hydrocarbon group, halogenated hydrocarbon group,substituted silyl group, alkoxy group or di-substituted amino group andthey may be the same or different; G⁺ represents an inorganic or organiccation; L represents a neutral Lewis base; and (L-H)⁺ represents aBrφnsted acid.

[0588] Such a catalyst for addition polymerization will be furtherillustrated in detail below.

[0589] (B) Aluminum Compounds

[0590] As the hydrocarbon group represented by E¹, E² and E³ in thealuminum compounds (B1), (B2) and (B3) mentioned above, respectively, ahydrocarbon group having 1 to 8 carbon atoms is preferable, and an alkylgroup is more preferable.

[0591] Specific examples of the organic aluminum compound (B1) of thegeneral formula E¹aAlZ_(3−a) include trialkylaluminums such astrimethylaluminum, triethylaluminum, tripropylaluminum,triisobutylaluminum, trihexylaluminum and the like; dialkylaluminumchlorides such as dimethylaluminum chloride, diethylaluminum chloride,dipropolyaluminum chloride, diisobutylaluminum chloride, dihexylaluminumchloride and the like; alkylaluminum dichlorides such as methylaluminumdichloride, ethylaluminum dichloride, propylaluminum dichloride,isobutylaluminum dichloride, hexylaluminum dichloride and the like;dialkylaluminum hydrides such as dimethylaluminum hydride,diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminumhydride, dihexylaluminum hydride and the like, etc.

[0592] Trialkylaluminums are preferable, and triethylaluminum ortriisobutylaluminum is more preferable.

[0593] As specific examples of E² and E³ in cyclic aluminoxanes (B2)having a structure of the general formula {—Al(E²)—O—}_(b), and linearaluminoxanes (B3) having a structure of the general formulaE³{—Al(E³)—O—}_(c)AlE³ ₂, respectively, alkyl groups such as a methylgroup, ethyl group, n-propyl group, isopropyl group, n-butyl group,isobutyl group, n-pentyl group, neopentyl group and the like can beexemplified. b in an integer of 2 or more, and c is an integer of 1 ormore. Preferably, E² and E³ are a methyl group or isobutyl group, b is 2to 40, and c is 1 to 40.

[0594] The above-mentioned aluminoxane is produced by various methods.The method is not particularly restricted, and it may be advantageouslycarried out according to a known method. For example, a trialkylaluminum(for example, trimethylaluminum) is dissolved in a suitable organicsolvent (benzene, aliphatic hydrocarbon or the like) to prepare asolution which is allowed to contact with water. Alternatively, there isexemplified a method in which a trialkylaluminum (for example,trimethylaluminum) is allowed to contact with a metal salt containingcrystal water (for example, copper sulfate hydrate or the like).

[0595] The aluminoxane produced by such methods is usually supposed tobe a mixtures of a cyclic aluminoxane and a linear aluminoxane.

[0596] (C) Boron Compound

[0597] As the boron compound (C), one or more boron compounds selectedfrom (C1) boron compounds of the general formula BQ¹Q²Q³, (C2) boroncompounds of the general formula G⁺(BQ¹Q²Q³Q⁴)⁻, and (C3) boroncompounds of the general formula (L-H)⁺(BQ¹Q²Q³Q⁴)⁻ are used, in thepresent invention.

[0598] In the boron compound (C1) of the general formula BQ¹Q²Q³, Brepresents a trivalent boron atom, and Q¹ to Q³ represent a halogenatom, hydrocarbon group, halogenated hydrocarbon group, substitutedsilyl group, alkoxygroupordi-substituted amino group, and they may bethe same or different. Q¹ to Q³ preferably represent a halogen atom, ahydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbongroup having 1 to 20 carbon atoms, a substituted silyl group having 2 to20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or anamino group having 1 to 20 carbon atoms, and Q¹ to Q³ more preferablyrepresent a halogen atom, a hydrocarbon group having 1 to 20 carbonatoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.Further preferably, Q¹ to Q⁴ represent a fluorinated hydrocarbon grouphaving 1 to 20 carbon atoms containing at least one fluorine atom, andparticularly preferably, Q¹ to Q⁴ represent a fluorinated aryl grouphaving 6 to 20 carbon atoms containing at least one fluorine atom.

[0599] Specific examples of the compound (C1) include

[0600] tris(pentafluorophenyl)borane,

[0601] tris(2,3,5,6-tetrafluorophenyl)borane,

[0602] tris(2,3,4,5-tetrafluorophenyl)borane,

[0603] tris(3,4,5-trifluorophenyl)borane,

[0604] tris(2,3,4-trifluorophenyl)borane,

[0605] phenylbis(pentafluorophenyl)borane and the like, andtris(pentafluorophenyl)borane is most preferable.

[0606] In the boron compound (C2) of the general formula G⁺(BQ¹Q²Q³Q⁴)⁻,G⁺ represents an inorganic or organic cation, B represents a trivalentboron atom, and Q¹ to Q⁴ are as defined for Q¹ to Q³ in theabove-mentioned (C1).

[0607] As specific examples of an inorganic cation G⁺ in the compound ofthe general formula G⁺(BQ¹Q²Q³Q⁴), a ferrocenium cation,alkyl-substituted ferrocenium cation, silver cation and the like arelisted, and as specific examples of an organic cation G⁺ in thecompound, a triphenylmethyl cation and the like are listed. G⁺represents preferably a carbenium cation, and particularly preferably atriphenylmethyl cation. As (BQ¹Q²Q³Q⁴)⁻ there are listed

[0608] tetrakis(pentafluorophenyl)borate,

[0609] tetrakis(2,3,5,6-tetrafluorophenyl)borate,

[0610] tetrakis(2,3,4,5-tetrafluorophenyl)borate,

[0611] tetrakis(3,4,5-trifluorophenyl)borate,

[0612] tetrakis(2,3,4-trifluorophenyl)borate,

[0613] phenyltris(pentafluorophenyl)borate,

[0614] tetrakis(3,5-bistrifluoromethylphenyl)borate and the like.

[0615] As specific combinations thereof, ferroceniumtetrakis(pentafluorophenyl)borate,

[0616] 1,1′-dimethylferrocenium

[0617] tetrakis(pentafluorophenyl)borate, silver

[0618] tetrakis(pentafluorophenyl)borate,

[0619] tripheylmethyltetrakis(pentafluorophenyl)borate,

[0620] triphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)bora te, andthe like are listed, and

[0621] triphenylmethyltetrakis(pentafluorophenyl)borate is mostpreferable.

[0622] In the boron compound (C3) of the general formula(L-H)⁺(BQ1Q²Q³Q⁴)⁻,L represents a neutral Lewis base and (L-H)⁺represents a Brφnsted acid, B represents a trivalent boron atom, and Q¹to Q⁴ are as defined for Q¹ to Q³ in the above-mentioned Lewis acid(C1).

[0623] As specific examples of the Brφnsted acid (L-H)⁺ in the compoundof the general formula (L-H)⁺(BQ¹Q²Q³Q⁴)⁻, trialkyl-substitutedammoniums, N,N-dialkylaniliniums, dialkylammoniums, triarylphosphoniumsand the like are listed, and as (BQ¹Q²Q³Q⁴)⁻, the same moieties asdescribed above are listed.

[0624] As specific combinations thereof,

[0625] triethylammoniumtetrakis(pentafluorophenyl)borate,

[0626] tripropylammonium tetrakis(pentafluorophenyl)borate,

[0627] tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate,tri(n-butyl)ammonium

[0628] tetrakis(3,5-bistrifluoromethylphenyl)borate,

[0629] N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,

[0630] N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,

[0631] N,N-2,4,6-pentamethylaniliniumtetrakis(pentafluorophenyl) borate,

[0632]N,N-dimethylaniliniumtetrakis(3,5-bistrifluoromethylphenyl)borate,

[0633] diisopropylammoniumtetrakis(pentafluorophenyl)borate,

[0634] dicyclohexyammoniumtetrakis(pentafluorophenyl)borate,

[0635] triphenylphosphoniumtetrakis(pentafluorophenyl)borate,

[0636] tri(methylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate,

[0637] tri(dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl) borateand the like are listed, and most preferable is tri(n-butyl)ammoniumtetrakis (pentafluorophenyl)borate, orN,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate.

[0638] Contact in preparation of a catalyst for addition polymerizationby bringing the transition metal compound (A) into contact with aco-catalyst for activation in the present invention may be conducted byany means providing the transition metal compound (A) and theco-catalyst for activation are contacted to form a catalyst, and thereare adopted a method in which a transition metal compound and aco-catalyst for activation are previously diluted with a solvent or notdiluted, before they are mixed for mutual contact, and a method in whicha transition metal compound and a co-catalyst for activation areseparately fed into a polymerization vessel for mutual contact thereof.As the co-catalyst for activation, a plurality of compounds may becombined and used, however, it is needless to say that a part of whichmay be previously mixed and used, or they may be separately fed into apolymerization vessel and used.

[0639] It is desirable to use components so that the molar ratio of thealuminum compound (B)/transition metal compound (A) is from 0.1 to10000, preferably from 5 to 2000, and the molar ratio of the boroncompound (C) /transition metal compound (A) is from 0.01 to 100,preferably from 0.5 to 10.

[0640] The concentrations of components when they are used in the formof a solution, or suspension or slurry in a solvent are appropriatelyselected depending on the ability of an apparatus for feeding componentsinto apolymerization reactor, and it is generally desirable that theconcentration of the transition metal compound (A) is usually from 0.001to 200 mmol/L, more preferably from 0.001 to 100 mmol/L, furtherpreferably from 0.05 to 50 mmol/L, the concentration of the aluminumcompound (B) is, in terms of an Al atom, usually from 0.01 to 5000mmol/L, more preferably from 0.1 to 2500 mmol/L, further preferably 0.1to 2000 mmol/L, and the concentration of the boron compound (C) isusually from 0.001 to 500 mmol/L, more preferably from 0.01 to 250mmol/L, further preferably from 0.05 to 100 mmol/L.

[0641] [Polymerization]

[0642] In the present invention, a catalyst for addition polymerizationobtained by bringing the above-mentioned transition metal compound (A)into contact with the aluminum compound (B) and/or the boron compound(C) is used. When a catalyst for addition polymerization obtained bybringing the transition metal compound (A) into contact with thealuminum compound (B) is used, the above-mentioned aluminoxane (B2)and/or linear aluminoxane (B3) is preferably used as (B). As otherpreferable embodiment of the catalyst for addition polymerization,catalysts for addition polymerization obtained by contact of thetransition metal compound (A) and, the aluminum compound (B) and theboron compound (C) are listed, and the above-mentioned (B1) is easilyused as (B) in this case.

[0643] As monomer applicable in polymerization, addition polymerizablecompounds such as olefins having 2 to 20 carbon atoms, particularly,ethylene, α-olefins having 3 to 20 carbon atoms, diolefins having 4 to20 carbon atoms, and the like can be used, and two or more monomers canbe used simultaneously. Specific examples of the olefin include linearolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1,heptene-1, octene-1, nonene-1, decene-1 and the like, branched olefinssuch as 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1,5-methyl-hexene-1 and the like, and diolefins such as 1,3-butadiene andisoprene, and vinylcyclohexane are also listed, however, the presentinvention should not be limited by these compounds. As specific examplesof combinations of monomers in conducting copolymerization, ethylene andpropylene, ethylene and butene-1, ethylene and hexene-1, ethylene andoctane-1, ethylene and 5-hexene-1-ol, propylene and butene-1,ethylene-vinylcyclohexane, and the like are exemplified, however, thepresent invention should not be limited by these combinations.

[0644] The polymerization method should also not be limitedparticularly, and for example, solvent polymerization using as a solventan aliphatic hydrocarbon such as butane, pentane, hexane, heptane,octane and the like, an aromatic hydrocarbon such as benzene, tolueneand the like, or a halogenated hydrocarbon such as methylene dichlorideand the like, or slurry polymerization, gas phase polymerization ingaseous monomers, and the like can be used, and any of continuouspolymerization and batch-wise polymerization is possible.

[0645] The polymerization temperature can be usually from −50 °C. to200° C., and particularly, preferably from −20° C. to 100° C., and thepolymerization pressure is usually preferably from normal pressure to 60kg/cm² G. The polymerization time is generally determined appropriatelydepending on the kind of the intended polymer, and the reactionapparatus, and usually, it can be from 1 minute to 20 hours. Further, inthe present invention, a chain transfer agent such as hydrogen or thelike can also be added for controlling the molecular weight of apolymer.

[0646] The following examples and comparative examples will illustratethe present invention further in detail below, but do not limit thescope of the present invention.

[0647] The properties of polymers in examples were measured by thefollowing methods.

[0648] (1) Intrinsic viscosity [η]: It was measured by using aUbbellohde viscometer in a tetralin solution at 130° C.

[0649] (2) Content of repeating units derived from α-olefin in acopolymer:

[0650] It was measured from the specific absorptions of ethylene andα-olefin using an infrared spectrophotometer (IR-810, manufactured byNippon Bunko Kogyo K.K.), and represented in terms of short chain branch(SCB) numbers per 1000 carbons. In addition, in a content of a comonomerother than α-olefin, the content was measured in the same manner.

[0651] (3) Melting point of copolymer: It was measured by using SeikoSSC-5200 under the following conditions.

[0652] Heating: 40° C. to 150° C. (10° C./min.), kept for 5 minutes

[0653] Cooling: 150° C. to 10° C. (5° C./min.), kept for 10 minutes

[0654] Measurement: 10° C. to 160° C. (5° C./min.)

[0655] (4) Molecular weight and molecular weight distribution: Thesewere measured by using gel permeation chromatography (manufactured byWaters, 150, C.) under the following conditions.

[0656] Column: TSK gel GMH-HT

[0657] Measurement temperature: set at 145° C.

[0658] Measurement concentration: 10 mg/10 ml-orthodichlorobenzene

[0659] The molecular weight distribution was evaluated by the ratio(Mw/Mn) of the weight average molecular weight (Mw) to the numberaverage molecular weight (Mn).

EXAMPLE 1

[0660] (1) Synthesis of 1-bromo-3-tert-butyl-5-methyl-2-phenol

[0661] In a 500 ml four-necked flask equipped with a stirrer, 20.1 g(123 mmol ) of 2-tert-butyl-4-methylphenol was dissolved in 150 ml oftoluene, subsequently, 25.9 ml (18.0 g, 246 mmol) of tert-butylamine wasadded to the solution, under nitrogen atmosphere. This solution wascooled to −70° C., to this was added 10.5 ml (32.6 g, 204 mmol) ofbromine. This solution was stirred for 2 hours while maintaining at −70°C. Subsequently, the solution was heated to room temperature, and washedwith 100 ml of 10% hydrochloric acid three times. After washing, theresulted organic layer was dried by anhydrous sodium sulfate, thesolvent was removed by using an evaporator, then, the layer was purifiedusing a silica gel column, to obtain 18.4 g (75.7 mmol) of colorlessoil: 1-bromo-3-tert-butyl-5-methyl-2-phenol. The yield was 62%.

[0662] (2) Synthesis of 1-bromo-3-tert-butyl-2-methoxy-5-methylbenzene

[0663] In a 100 ml four-necked flask equipped with a stirrer, 13.9 g(57.2 mmol) of 1-bromo-3-tert-butyl-5-methyl-2-phenol synthesized in (1)above was dissolved in 40 ml of acetonitrile, subsequently, 3.8 g (67.9mmol) of potassium hydroxide was added to the solution, under nitrogenatmosphere. Further, 17.8 ml (40.6 g, 286 mmol) of methyl iodide wasadded, and the mixture was stirred continuously for 12 hours. Then, thesolvent was removed by using an evaporator, 40 ml of hexane was added tothe residue, and hexane soluble portions were extracted. The extractionwas repeated three rimes. The solvent was removed from the extractedfraction, to obtain 13.8 g (53.7 mmol) of pale yellow oil:1-bromo-3-tert-butyl-2-methoxy-5-methylbenzene. The yield was 94%.

[0664] (3) Synthesis of chlorodimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silane

[0665] Into a solution composed of 31.5 ml of tetrahydrofuran, 139 ml ofhexane and 45 g of 1-bromo-3-tert-butyl-2-methoxy-5-methylbenzenesynthesized in the same method as in the above-mentioned process (2) wasadded 115 ml of a 1.6 mol/liter solution of n-butyllithium in hexanedropwise at −40° C. over 20 minutes. The resulted mixture was kept at−40° C. for 1 hour, then, 31.5 ml of tetrahydrofuran was added dropwise.

[0666] Into a solution composed of 131 g of dichlorodimethylsilane and306 ml of hexane was added the mixture obtained above dropwise at −40°C. The resulted mixture was heated up to room temperature over 2 hours,further, stirred for 12 hours at room temperature.

[0667] From the reaction mixture, the solvent and excessdichlorodimethylsilane were distilled off under reduced pressure, andhexane-soluble portions were extracted from the residue using hexane,and the solvent was distilled off from the resulted hexane solution, toobtain 41.9 g of chlorodimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silane in the form of pale yellow oil. The yield was 84%.

[0668] (4) Synthesis of (tetramethylcyclopentadienyl)dimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silane

[0669] Into a solution composed of 5.24 g ofchlorodimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)sila ne synthesizedin (3) above and 50 ml of tetrahydrofuran was added 2.73 g oftetramethylcyclopentadienyllithium dropwise at −35° C., and the mixturewas heated up to room temperature over 2 hours, and further stirred for10 hours at room temperature.

[0670] The solvent was distilled off under reduced pressure from theresulted reaction mixture, and hexane-soluble portions were extractedfrom the residue using hexane, and the solvent was distilled off underreduced pressure from the resulted hexane solution, to obtain 6.69 g of(tetramethylcyclopentadienyl)dimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silanein the form of yellow oil. The yield was 97%.

[0671] (5) Synthesis of[dimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silyl(tetramethylcyclopentadienyl)]titanium dichloride Into a solutioncomposed of 2.00 g of(tetramethylcyclopentadienyl)dimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silanesynthesized in (4) above, 20 g of toluene and 1.25 g of triethylaminewas added 3.84 ml of a 1.61 mol/liter solution of n-butyllithium inhexane dropwise at 0° C., then, the solution was heated up to roomtemperature over 2 hours, further maintained at room temperature for 12hours.

[0672] 20.9 g of suspension of 2.09 g of titanium trichloridetripyridine in toluene was added dropwise at 0° C. under nitrogenatmosphere into the mixture obtained above, then, the mixture was heatedup to room temperature over 1 hour, then, the mixture was heated underreflux for 10 hours.

[0673] The reaction mixture was filtrated, the solvent was distilled offfrom the filtrate, and the residue was re-crystallized from atoluene-hexane mixed solvent, to obtain 0.46 g of[dimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silyl(tetramethylcyclopentadienyl)]titaniumdichloride in the form of a pale green fine crystal. The yield was 17%.

[0674] The spectral data is as shown below.

[0675] Mass spectrum (CI, m/e) 473

[0676] An autoclave having an inner volume of 1 liter equipped with astirrer as a reactor was dried under vacuum and purged with argon, then,300 ml of toluene as a solvent was charged therein, and the reactor washeated up to 60° C. After the heating, ethylene was fed whilecontrolling the ethylene pressure at 6 kg/cm², and after the system wasstabilized, 1.0 mmol of triisobutylaluminum was added, subsequently, 2.0μmol of[dimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silyl(tetramethylcyclopentadienyl)]titaniumdichloride synthesized in (5) above was added, then, 6.0 μmol oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate was added.Polymerization was carried out for 60 minutes while controlling thetemperature at 60° C. The temperature in the reactor increased by 3.1°C. by the initial heat generation in this polymerization.

[0677] As a result of polymerization, an ethylene homopolymer having amelting point of 133.1° C. was produced at a rate of 8.7×10⁶ g per onehour per 1 mol of the titanium compound.

EXAMPLE 2

[0678] An autoclave having an inner volume of 0.4 liter equipped with astirrer as a reactor was dried under vacuum and purged with argon, then,190 ml of toluene as a solvent and 10 ml of hexene-1 as an α-olefin werecharged into this, and the reactor was heated up to 60° C. Aftertemperature raise, ethylene was fed while controlling the ethylenepressure at 6 kg/cm², and after the system was stabilized, 0.5 mmol oftriisobutylaluminum was added, subsequently, 1.0 μmol of[dimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silyl(tetramethylcyclopentadienyl)]titaniumdichloride was added, then, 3.0 μmol oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate was added.Polymerization was carried out for 60 minutes while controlling thetemperature at 60° C. The temperature in the reactor increased by 1.9°C. by the initial heat generation in this polymerization.

[0679] As a result of polymerization, an ethylene-hexene-1 copolymerhaving an SCB of 20.6, a [η] of 1.17 dl/g, a molecular weight (Mw) of7.6×10⁴, a molecular weight distribution (Mw/Mn) of 2.2 and a meltingpoint of 110.3° C. was produced at a rate of 1.5×10⁷ g per one hour per1 mol of the titanium compound.

Comparative Example 1

[0680] An autoclave having an inner volume of 0.4 liter equipped with astirrer as a reactor was dried under vacuum and purged with argon, then,190 ml of toluene as a solvent and 10 ml of hexene-1 as an α-olefin werecharged into this, and the reactor was heated up to 60° C. After theheating, ethylene was fed while controlling the ethylene pressure at 6kg/cm², and after the system was stabilized, 0.50 mmol oftriisobutylaluminum was added, subsequently, 1.0 μmol of[dimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silyl(tetramethylcyclopentadienyl)]titaniumdichloride was added, then, 3.0 μmol oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate was added.Polymerization was carried out for 60 minutes while controlling thetemperature at 60° C. The temperature in the reactor increased by 11.5°C. by the initial heat generation in this polymerization.

[0681] As a result of polymerization, an ethylene-hexene-1 copolymer wasproduced at a rate of 1.1×10⁷ g per one hour per 1 mol of the titaniumcompound.

EXAMPLE 3

[0682] An autoclave having an inner volume of 0.4 liter equipped with astirrer as a reactor was dried under vacuum and purged with argon, then,190 ml of toluene as a solvent and 10 ml of hexene-1 as an α-olefin werecharged into this, and the reactor was heated up to 60° C. Aftertemperature raise, ethylene was fed while controlling the ethylenepressure at 6 kg/cm2 , and after the system was stabilized, an MMAO type3A toluene solution manufactured by Tosoh-Akzo Company, Ltd., wascharged in an amount of 1.0 mmol in terms of Al, subsequently, 1.0 μmolof[dimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silyl(tetramethylcyclopentadienyl)]titaniumdichloride was added. Polymerization was carried out for 60 minuteswhile controlling the temperature at 60° C. The temperature raise in thereactor by the initial heat generation in this polymerization was notobserved.

[0683] As a result of polymerization, an ethylene-hexene-1 copolymerhaving an SCB of 14.8, a [η] of 1.71 dl/g, a molecular weight (Mw) of7.1×10⁴, a molecular weight distribution (Mw/Mn) of 1.9 and a meltingpoint of 114.7° C. was produced at a rate of 3.1×10⁶ g per one hour per1 mol of the titanium compound.

EXAMPLE 4

[0684] Polymerization was carried out in the same manner as in Example 2except that hexane-1 used was changed to 10 g of butene-1. Thetemperature in the reactor increased by 2.6° C. by the initial heatgeneration in this polymerization.

[0685] As a result of polymerization, an ethylene-butene-1 copolymerhaving an SCB of 15.2, a [η] of 1.26 dl/g, a molecular weight (Mw) of7.5×10⁴, a molecular weight distribution (Mw/Mn) of 2.7 and a meltingpoint of 93.9° C. was produced at a rate of 1.5×10⁷ g per one hour per 1mol of the titanium compound.

EXAMPLE 5

[0686] Polymerization was carried out in the same manner as in Example 2except that triisobutylaluminum was changed to triethylaluminum of thesame molar amount. The temperature in the reactor increased by 0.3° C.by the initial heat generation in this polymerization.

[0687] As a result of polymerization, an ethylene-hexene-1 copolymerhaving an SCB of 12.7, a [η] of 1.23 dl/g, a molecular weight (Mw) of3.4×10⁴, a molecular weight distribution (Mw/Mn) of 2.2 and a meltingpoint of 116.8° C. was produced at a rate of 1.3×10⁷ g per one hour per1 mol of the titanium compound.

EXAMPLE 6

[0688] Polymerization was carried out in the same manner as in Example 2except that triisobutylaluminum was changed to trimethylaluminum of thesame molar amount. The temperature in the reactor increased by 0.4° C.by the initial heat generation in this polymerization.

[0689] As a result of polymerization, an ethylene-hexene-1 copolymerhaving an SCB of 9.6, a [η] of 2.13 dl/g, a molecular weight (Mw) of16.8×10⁴, a molecular weight distribution (Mw/Mn) of 8.3 and a meltingpoint of 119.9° C. was produced at a rate of 7.7×10⁶ g per one hour per1 mol of the titanium compound.

EXAMPLE 7

[0690] Polymerization was conducted in the same manner as in Example 2except that triphenylcarboniumtetrakis (pentafluorophenyl)borate waschanged to [dimethylanilinium][tetrakis(pentafluorophenyl)borate] of thesame molar amount. The temperature raise in the reactor by the initialheat generation in this polymerization was not observed.

[0691] As a result of polymerization, an ethylene-hexene-1 copolymerhaving an SCB of 18.6, and a melting point of 114.1° C. was produced ata rate of 1.9×10⁶ g per one hour per 1 mol of the titanium compound.

EXAMPLE 8

[0692] An autoclave having an inner volume of 1 liter equipped with astirrer as a reactor was dried under vacuum and purged with argon, then,300 ml of toluene as a solvent was charged into this, and the reactorwas heated up to 40° C. After the heating, propylene was fed whilecontrolling the propylene pressure at 4 kg/cm², and after the system wasstabilized, 1.25 mmol of triisobutylaluminum was added, subsequently,5.0 μmol of[dimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silyl(tetramethylcyclopentadienyl)]titaniumdichloride was added, then, 15.0 μm oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate was added.Polymerization was carried out for 60 minutes while controlling thetemperature at 40° C. The temperature in the reactor increased by 5.2°C. by the initial heat generation in this polymerization.

[0693] As a result of polymerization, a propylene homopolymer having amolecular weight (Mw) of 1.04×10⁶, a molecular weight distribution(Mw/Mn) of 2.2, a meso triad of 0.283 and a raceme triad of 0.162 wasproduced at a rate of 1.6×10⁶ g per one hour per 1 mol of the titaniumcompound.

EXAMPLE 9

[0694] A stirring rod was placed into an autoclave having an innervolume of 0.1 liter, then, the autoclave was dried under vacuum andpurged with argon, then, 25 ml of toluene as a solvent was charged intothis, PMAO-S manufactured by Tosoh-Akzo Company, Ltd., was charged in anamount of 6.0 mmol in terms of Al, subsequently, 6.0 μmol of[dimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silyl(tetramethylcyclopentadienyl)]titaniumdichloride was added. Into this was introduced 3.24 g of 1,3-butadiene,and polymerization was carried out for 60 minutes while controlling thetemperature at 25° C.

[0695] As a result of polymerization, a 1,3-butadiene homopolymer havinga molecular weight (Mw) of 4.6×10⁵, and a molecular weight distribution(Mw/Mn) of 2.8 (ratio of bonding mode of double bond parts in a polymerchain, [1,4-cis]:[1,4-trans]:[1,2-]=0.830:0.070:0.100) was produced at arate of 4.0×10⁴ g per one hour per 1 mol of the titanium compound.

EXAMPLE 10

[0696] An autoclave having an inner volume of 1 liter equipped with astirrer as a reactor was dried under vacuum and purged with argon, then,300 ml of toluene as a solvent and 1.0 ml of 5-hexene-1-ol as acomonomer were charged into this, and the reactor was heated up to 40°C. After the heating, 20 mmol of triethylaluminum was added, ethylenewas fed while controlling the ethylene pressure at 6 kg/cm², and themixture was stirred continuously for 15 minutes. After the system wasstabilized, 5.0 μmol of[dimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silyl(tetramethylcyclopentadienyl)]titanium dichloride was added, then, 15.0 μm oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate was added.Polymerization was carried out for 60 minutes while controlling thetemperature at 40° C. The temperature raise in the reactor by theinitial heat generation in this polymerization was not observed.

[0697] As a result of polymerization, an ethylene-hexene-1-ol copolymerhaving a terminal alcohol content of 0.68 wt % and an [η] of 4.96 dl/gwas produced at a rate of 1.2×10⁵ g per one hour per 1 mol of thetitanium compound.

EXAMPLE 11

[0698] An autoclave having an inner volume of 1 liter equipped with astirrer as a reactor was dried under vacuum and purged with argon, then,300 ml of toluene as a solvent and 15 ml of vinylcyclohexane as anα-olefin were charged into this, and the reaction vessel was heated upto 60° C. After the heating, ethylene was fed while controlling theethylene pressure at 6 kg/cm², after the system was stabilized, 0.75mmol of triisobutylaluminum and 1.5 μmol of[dimethyl(3-tert-butyl-2-methoxy-5-methylphenyl)silyl(tetramethylcyclopentadienyl)]titaniumdichloride were added, then, 4.5 μmol oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate was added.Polymerization was conducted for 60 minutes while controlling thetemperature at 60° C. The temperature raise in the reactor by theinitial heat generation in this polymerization was not observed.

[0699] As a result of polymerization, an ethylene-vinylcyclohexanecopolymer having a content of a vinylcyclohexane unit of 4.1 wt %, an[η] of 2.27 dl/g was produced at a rate of 1.9×10⁶ g per one hour per 1mol of the titanium compound.

[0700] As described in detail above, according to the present invention,a transition metal compound useful for preparing a catalyst for additionpolymerization having a catalytic activity which suppresses heatgeneration at the beginning of polymerization and can be industriallycarried out, such a catalyst for addition polymerization, and a processfor producing an addition polymer with the catalyst, are provided.

1. A transition metal compound represented by the general formula (1):

wherein M represents a titanium atom, zirconium atom or hafnium atom inthe +3 formal oxidation state; A represents a multidentate mono-anionicligand; R¹ represents an alkyl group, aralkyl group, aryl group orsubstituted silyl group; E represents an oxygen atom or sulfur atom;each of two Xs independently represents a hydrogen atom, halogen atom,alkyl group, aralkyl group, aryl group, substituted silyl group, alkoxygroup, aralkyloxy group, aryloxy group or di-substituted amino group,and two Xs may bond mutually to form a ring; D represents a neutralligand coordinated on M; and n represents an integer of from 0 to
 2. 2.The transition metal compound according to claim 1, wherein A representsa multidentate mono-anionic ligand of the general formula (2):

wherein Cp¹ represents a group having a cyclopentadiene type anionskeleton; and G represents a substituent having 1 to 30 non-hydrogenatoms bridging between Cp¹ and E.
 3. The transition metal compoundaccording to claim 1, wherein the transition metal compound isrepresented by the general formula (3):

wherein M represents a titanium atom, zirconium atom or hafnium atom inthe +3 formal oxide condition; Cp¹ represents a group having acyclopentadiene type anion skeleton; J represents an atom of XIV groupin the periodic table of element; each of R² and R³ independentlyrepresents a hydrogen atom, halogen atom, alkyl group, aralkyl group,aryl group, substituted silyl group, alkoxy group, aralkyloxy group,aryloxy group or di-substituted amino group, and a plurality of R²s maybond mutually to form a ring; m represents an integer of from 0 to 4; Erepresents an oxygen atom or sulfur atom; R¹ represents an alkyl group,aralkyl group, aryl group or substituted silyl group; each of two Xsindependently represents a hydrogen atom, halogen atom, alkyl group,aralkyl group, aryl group, substituted silyl group, alkoxy group,aralkyloxy group, aryloxy group or di-substituted amino group, and twoXs may bond mutually to form a ring; D represents a neutral ligandcoordinated on M; and n represents an integer of from 0 to
 2. 4. Thetransition metal compound according to claim 1, wherein E represents anoxygen atom.
 5. The transition metal compound according to claim 3,wherein E represents an oxygen atom.
 6. The transition metal compoundaccording to claim 1, wherein M represents a titanium atom.
 7. Thetransition metal compound according to claim 3, wherein M represents atitanium atom.
 8. The transition metal compound according to claim 1,wherein R¹ represents a methyl group.
 9. The transition metal compoundaccording to claim 3, wherein R¹ represents a methyl group.
 10. Acatalyst for addition polymerization obtained by a process comprisingbringing the following (A) into contact with the following (B) and/orthe following (C): (A) a transition metal compound represented by thegeneral formula (1):

 wherein M represents a titanium atom, zirconium atom or hafnium atom inthe +3 formal oxidation state; A represents a multidentate mono-anionicligand; R¹ represents an alkyl group, aralkyl group, aryl group orsubstituted silyl group; E represents an oxygen atom or sulfur atom;each of two Xs independently represents a hydrogen atom, halogen atom,alkyl group, aralkyl group, aryl group, substituted silyl group, alkoxygroup, aralkyloxy group, aryloxy group or di-substituted amino group,and two Xs may bond mutually to form a ring; D represents a neutralligand coordinated on M; and n represents an integer of from 0 to 2, (B)one or more aluminum compounds selected from the following (B1) to (B3):(B1) organic aluminum compounds of the general formula E¹ _(a)AlZ_(3-a),(B2) cyclic aluminoxanes having a structure of the general formula{—Al(E²)—O—}_(b), and (B3) linear aluminoxanes having a structure of thegeneral formula E³{—Al(E³)—O—}_(c)AlE³ ₂, wherein each of E¹, E² and E³represents a hydrocarbon group, and all E¹s, all E²s or all E³s may bethe same or different; Z represents a hydrogen atom or halogen atom andall Zs may be the same or different; a represents a number satisfying0<a≦3, b represents an integer of 2 or more; and c represents an integerof 1 or more, (C) one or more boron compounds selected from thefollowing (C1) to (C3): (C1) boron compounds of the general formulaBQ¹Q²Q³, (C2) boron compounds of the general formula G⁺(BQ¹Q²Q³Q⁴)⁻, and(C3) boron compounds of the general formula (L-H)⁺(BQ¹Q²Q³Q⁴)⁻, whereinB represents a trivalent boron atom; Q¹ to Q⁴ represent a halogen atom,hydrocarbon group, halogenated hydrocarbon group, substituted silylgroup, alkoxygroupordi-substituted amino group and they may be the sameor different; G⁺ represents an inorganic or organic cation; L representsa neutral Lewis base; and (L-H)⁺ represents a Brφnsted acid.
 11. Thecatalyst according to claim 10, wherein the A represents a multidentatemono-anionic ligand of the general formula (2):

wherein Cp¹ represents a group having a cyclopentadiene type anionskeleton; and G represents a substituent having 1 to 30 non-hydrogenatoms bridging between Cp¹ and E.
 12. The catalyst according to claim10, wherein the transition metal compound (A) is represented by thegeneral formula (3):

wherein M represents a titanium atom, zirconium atom or hafnium atom inthe +3 formal oxidation state; Cp¹ represents a group having acyclopentadiene type anion skeleton; J represents an atom of XIV groupin the periodic table of element; each of R² and R³ independentlyrepresents a hydrogen atom, halogen atom, alkyl group, aralkyl group,aryl group, substituted silyl group, alkoxy group, aralkyloxy group,aryloxy group or di-substituted amino group, and a plurality of R²S maybond mutually to form a ring; m represents an integer of from 0 to 4; Erepresents an oxygen atom or sulfur atom; R¹ represents an alkyl group,aralkyl group, aryl group or substituted silyl group; each of two Xsindependently represents a hydrogen atom, halogen atom, alkyl group,aralkyl group, aryl group, substituted silyl group, alkoxy group,aralkyloxy group, aryloxy group or di-substituted amino group, and twoXs may bond mutually to form a ring; D represents a neutral ligandcoordinated on M; and n represents an integer of from 0 to
 2. 13. Thecatalyst according to claim 10, wherein M is a titanium atom.
 14. Thecatalyst according to claim 12, wherein M is a titanium atom.
 15. Thecatalyst according to claim 10, R¹ represents a methyl group.
 16. Thecatalyst according to claim 12, R¹ represents a methyl group.
 17. Aprocess for producing an addition polymer which comprising polymerizingan addition polymerizable hydrocarbon compound with the catalyst foraddition polymerization of claim
 10. 18. A process for producing anaddition polymer which comprising polymerizing an addition polymerizablehydrocarbon compound with the catalyst for addition polymerization ofclaim 12.